Plasticizer and process of producing same



Patented Oct. 11, 193

UNlT EDj- STATES 2,132,724 rms'rrorzaa AND PROCESS or rnonveme sum;

Harold R. Dalton, Teaneck, N. J., assignor to John S. Ware, New.York, N. Y., ilfosephll. mete,-

Chappaqua, N. Y., and

Application December 9, 1936, Serial No. 114,927

No Drawing.

4' Claims. (01. 91-68) This invention relates to plasticizing agents of the saccharide type, and to the method of producing same.

, One object of the invention is to produce a 5 plasticizing agent of this nature which is highly eflicient, inexpensive to manufacture and which produces permanent plasticizing efiects.

Another object of the invention is to produce such'a plasticizing agent which comprises a wa- IO ter solution of a saccharide or combination of saccharides and reduction products of these saccharides such as sorbitol mannitol, glycol, etc.

A further object] of the invention. isthe provision of a method of producing such a plasticiz- 5 ing agent which consists of partially reducing a water solution of invert sugar to the state wherein itis broken up into water, invert sugar, sorbitol, mannitol andother reduction products.

Other objects and advantages of my improved 20 plasticizing agent and the method of producing same will become more apparent as the description proceeds.

The disclosure made the basis of exemplifying the present inventivevconcept suggests a practical 25 embodiment thereof,'but the invention is notto be restricted to the exact, details of this disclosure, and the latter, therefore, is to be under- 1 stood from an illustrative, rather than a 'restrictive standpoint.

30 At the present time the'use of a water solution of invert sugar as a'plasticizer in the manufacture of paper, flexible glue and products such as gaskets and adhesives for gummed paper which I employ glue in their manufacture, does not give 35 altogether satisfactory results unless a small per- .centage of some other material is used along with it. The chief reason for this failure of water solutions of invert sugar to act as a satisfactory papergradually loses its flexibility and becomes brittle. Also paper which has had too much moisture removed from it during' drying on the paper machine, will come off the machine in a brittle condition as a result of the crystallization of the dextrose. In the case of glue products this crystallization proceeds at relative humidities as high as 65%. In a flexible glue the crystals very .55 quickly cover the surface of the material and gradually penetrate through the entire mass. -Here.agai n the crystallization is accompanied by increasing brittleness. In the case of glue products which vhave become brittle as a result of the crystallization of the dextrose, conditioning at high relative humidities has little effect in bringing them back to their original state.

The above mentioned crystallization may be overcome by the addition of 20% to 30% of glycerine, by weight, to an invert sugar solution containing Ti invert sugar (dry weight). Ethylene glycol in some cases is substituted for the glycerine. When using ethylene glycol, the percentage may vary somewhat from the to ratio found necessary when glycerine is used.

, Such additions, however, increase the cost of the product. 1,

Since water solutions of invert sugar are not satisfactory'in themselves for producing lasting and satisfactory plasticizing effects, I carried on 20 extensive investigations as to the best manner of treating such solutions so that they may be modified for satisfactory use as a plasticizer.

The aforementioned investigations resulted in the development of a partially reduced invert 25 sugar solution which gave highly satisfactory results when used as aplasticizer. This plasticizer, which will hereafter be termed partially reduced invert sugar plasticizer, was readily and economically prepared by the two methods described be- 3 low:

1. Reduction with sodium amalgam.--A water solution of invert sugar containing 76.0% invert sugar by weight was treated with 2 sodium amalgam. Equal weight of amalgam and invert sugar solution were used. The amalgam was added in small quantities. The reaction mixture was vigorously and continuously stirred until all of the amalgam was used up. The temperature of the mixture was maintained at 30 C. by plac- 40 ing the container in a water bath regulated to maintain this temperature. Sulphuric acid wasadded in small portions during the reaction in order to maintain the mixture neutral. The I yield of reduced material was approximately 7.0%. :1 i

- 2. Reduction with nickel in rm atmosphere of hydrogen.-A water solution of invert sugar .containing 77.0% invert sugar by weight was placed in an autoclave containing catalytic nickel. -The air was swept out of the chamber with hydrogen. The hydrogen pressure in the autoclave was finally.-raised 120.1500 lbs./sq. in. The mixture in the autoclave was stirred for four hours, the pressure of hydrogen being maintained at 1500 lbs./

occur.

sq. in. and the temperature at approximately 35 C.

- 'The catalytic nickel was prepared from nickel formate reduced with hydrogen at 300 C.

The yield of reduced material was approximately 25%, consisting principally of sorbitol and mannitol.

Other methods of reduction such as electrolytic and those employing zinc, magnesium, etc. can

ucts will be maintained in a stable plasticized state, and no tendency to become brittle will I have also found that in a plasticizer suitable for commercial use the ingredients may vary about as follows:

Invert sugar, glucose or fructose, etc., from a minimum of 50% to a maximum of water from a minimum of 10% to a maximum of 30% and reduced materials (mixture of sorbitol, mannitol and other reduced products) from 5% to 30%.

Partially reduced invert sugar plasticizer of a composition falling within the above range of compositions can be made by a slight variation of the method described. Thus glucose, fructose, xylose', sorbose, mannose, arabinose, etc., may be reduced by either of the methods described above and to the reduced product sufficlent invert sugar added to give a composition falling within the range specified.

A polysaccharide, like cane sugar (sucrose) or molasses, may be used as a starting material, inversion and reduction being made to take place simultaneously. In this method the plasticizer may contain a small percentage of cane sugar.

As a final method of preparation, sorbitol and mannitol, which'will contain other reduction products, may be isolated from a reduced sugar mixture and added to an invert sugar solution to give a solution having a compositionfalling within the above mentioned range.

A highly satisfactory plasticizer made in accordance with my invention would comprise the following ingredients in about the proportions specified:

Per cent Invert sugar .4... 50 Water 7 25 Reduced materials 25 It is also possible to produce-a satisfactory plasticizer by the addition of 25 lbs. of a mixture of commercial sorbitol and mannitol to 75 lbs. of invert sugar.

In producing sorbitol and mannitol commereially, it is possible that certain aforementioned reduction products may not be present in the commercial product, but I find that in my product these materials contribute greatly to the production of a more eflicient plasticizer.

,I have found that it is more economical to produce the sorbitol and mannitol directly in the invert sugar in about the proportions indicated, than to independently produce and refine each constituent and subsequently mix them.

I also find that a mixture such as mentioned above will make a more efficient plasticizer because it produces more stable and more lasting results when used as a plasticizer for paper, fabrics, glue and the like. This is particularly true when compared with the usual mixture of invert sugar and glycerine which is a common compound for such purposes.

Wherever in the specification and in the claims I have used the term invert sugar, I desire it understood that any mono-saccharide is to be included.

Having described my invention, what I claim as new and desire to secure by Letters Patent is:

1. A plasticizer for paper and the like comprising a water solution of invert sugar, and the reaction products formed by. partially reducing a water solutionof invert sugar, said 'reaction products including sorbitol and mannitol the ratio by weight of the invert sugar to the reaction products being approximately as .2 is to 1, said reaction products serving to prevent crystallization of the unreduced sugar.

2. A plasticizer for paperand the like comprising a water solution of invert sugar, and the reaction products formed bypartially reducing a water solution of invert sugar, said reaction products including sorbitol and mannitol, the ratio by weight of the various ingredients being approximately as fo llowszinvert sugar 50 per. cent, reaction products 25 per cent, water 25 per cent.

3. As a new article of manufacture, fibrous material impregnated and plasticized with a water solution of invert sugar in major proportion and the reaction products formed by partially reducing the water solution of invert sugar,

said reaction products including sorbitol and I mannitol, and said reaction products being in sufficient amount to prevent, crystallization of the unreduced sugar.

4. Asa new article of manufacture, paper impregnated with a water solution of invert sugar and the reaction products formed by partially hydrogenizing a water solution of invert sugar, ,said reaction products including sorbitol and HAROLD R. DALTON. 

